Compounds by addition of hydroperoxides to α-β-unsaturated ketones

Abstract

Compounds containing at least one keto group and at least one peroxy group, each peroxy oxygen being joined to a tertiary carbon atom. Examples: 2-Methyl-2-(t-butylperoxy)-4-pentanone. 2,6-Dimethyl-2,6-bis(t-butylperoxy)-4-heptanone. 3,5,5-Trimethyl-3-(t-butylperoxy)cyclohexanone. The compounds are prepared by the strong acid catalyzed addition of a tertiary hydroperoxide to an α,β-unsaturated ketone. Illustration: Mesityl oxide and pinanyl hydroperoxide, in slight excess, were reacted at 0° C. in the presence of 77% sulfuric acid; the reaction mix was stirred for 16 hours at 25° C. Product 2-methyl-2-pinanylperoxy-4-pentanone was recovered.

Thus, having described the invention, what is claimed is: 
     
       1. 2-Methyl-2-(t-butylperoxy)-4-pentanone. 
     
     
       2. 2,6-Dimethyl-2,6-bis(t-butylperoxy)-4-heptanone. 
     
     
       3. 2,15-Dioxo-4,4,7,7,10,10,13,13-octamethyl-5,6,11,12-tetraoxa-8-hexadecyne. 
     
     
       4. 2-Methyl-2-(4-t-butylperoxy-1,1,4,4-tetramethylbutylperoxy)-4-pentanone. 
     
     
       5. 2-Methyl-2-cumylperoxy-4-pentanone. 
     
     
       6. A process comprising intermingling mesityl oxide, about 3 moles, and t-butyl hydroperoxide, about 2.4 moles, to about 20° C. while adding about 27 grams of 70% sulfuric acid thereto; heating said intermingled mixture to about 40° C. over a period of about 1 hour and continuing said reaction for about 2 hours; and recovering 2-methyl-2-(t-butylperoxy)-4-pentanone from the product mixture. 
     
     
       7. Keto-peroxy compounds of the formula: ##STR24## where: (a) said compound includes at least one peroxy (--OO--) group and at least one keto ##STR25##  group; (b) m and n are each integers equal to 0-2 and m+n equals 2; (c) Z is a biradical selected from Q, Q--OO--Q, ##STR26##  Q--OO--R 5  --OO--Q, ##STR27## (d) Q is the biradical ##STR28##  where the t-carbon atom is joined to a peroxy oxygen; (e) said ##STR29##  group has at least one valence joined to a carbon atom α to the t-carbon atom in Q;   (f) R 1 , R 2  and R 4  are each selected from alkyl having 1-12 carbons; phenalkyl having 7-20 carbons; phenyl; and cycloalkyl having 4-20 carbons, R 1  and R 2  not both being phenyl;   (g) R 3  is selected from C 4  -C 10  alkyl, cycloalkyl, phenalkyl and corresponding radicals containing a halo, hydroxy or alkylperoxy substituent, said radicals affording a t-carbon atom which is joined to a peroxy oxygen atom; and   (h) R 5  is selected from C 7  -C 20  alkylene, alkenylene, alkynylene, and alkylenephenalkylene biradicals affording two t-carbon atoms which are joined to different peroxy groups.   
     
     
       8. A process for preparing a keto-peroxy compound which process comprises: (a) contacting an α, β-unsaturated ketone selected rom ##STR30##  a hydroperoxide selected from R 3  OOH and HOOR 5  OOH, and a catalytic amount of a strong acid at a temperature of between about 0° C. and about 80° C., and   (b) recovering a keto-peroxy product, where R 1 , R 2 , R 3 , R 4  and R 5  are as defined in claim 7.   
     
     
       9. Claim 8 where (a) is performed in a solvent selected from diethyl ether and pentane. 
     
     
       10. Keto-peroxy compounds of the formula: ##STR31## where: (a) Z is a biradical selected from Q, Q--OO--Q, Q--OO--R 5  --OO--Q, ##STR32## (b) the ##STR33##  groups have at least one valence joined to a carbon atom α to the t-carbon atom in Q; and (c) Q, R 1 , R 2 , R 3 , R 4  and R 5  are as defined in claim 7.   
     
     
       11. An organic peroxide prepared by reacting (A) cumene hydroperoxide and (B) an alpha-beta unsaturated ketone selected from the group consisting of mesityl oxide, phorone and isophorone, at a mol ratio ranging from about 4:1 to about 1:2.4 in the presence of (C) sulfuric acid at a temperature ranging from about 0° C. to about 80° C. 
     
     
       12. An organic peroxide according to claim 11 wherein the temperature of the reaction ranges from about 25° C. to about 35° C. 
     
     
       13. An organic peroxide according to claim 11 wherein the mole ratio of (A) to (B) ranges from about 1:1 to about 1:2. 
     
     
       14. An organic peroxide according to claim 11 wherein the reaction is carried out in the absence of a solvent. 
     
     
       15. An organic peroxide according to claim 11 wherein a solvent is used for the reaction. 
     
     
       16. An organic peroxide namely 4-cumylperoxy-4-methyl-2-pentanone. 
     
     
       17. An organic peroxide; namely, 4-t-butylperoxy-4-methyl-2-pentanone. 
     
     
       18. An organic peroxide; namely 4-t-amylperoxy-4-methyl-2-pentanone.